Experiment No.

Aim: To study Simultaneous Thermal Analysis of various samples

Objectives:

1. To study the change in mass of material with respect to temperature

2. To study the heat flow within the material with respect to temperature

Under controlled atmosphere and heating rate.

Introduction: Simultaneous Thermal Analysis (STA) generally refers to the simultaneous application of

Thermogravimetry (TGA) and Differential Scanning Calorimetry (DSC) to one and the same sample in a
single instrument. Simultaneous TGA/DSC measures both heat flow (DSC) and weight changes (TGA) in a
material as a function of temperature or time in a controlled atmosphere. Simultaneous measurement
of these two material properties not only improves productivity but also simplifies interpretation of
the results. The complimentary information obtained allows differentiation between endothermic and
exothermic events which have no associated weight loss (e.g., melting and crystallization) and those
which involve a weight loss (e.g., degradation).

A calorimeter measures the heat into or out of a sample. A differential calorimeter measures the heat
of a sample relative to a reference. A DSC does all of these activities and heats the sample with a linear
temperature ramp. In case of endothermic reaction, heat flows into the sample and for exothermic
reaction, heat flows out of the sample. DSC measures the temperatures and heat flows associated with
transitions in materials as a function of time and temperature in a controlled atmosphere. These
measurements provide quantitative and qualitative information about physical and chemical changes
that involve endothermic or exothermic processes, or changes in heat capacity.

Fig. 1 Schematic diagram of a heat flux differential scanning calorimeter (DSC).

A thermogravimetric analysis is also possible in this equipment. It continuously measures mass while the
temperature of a sample is changed over time. The thermogravimetric data collected from a thermal
reaction is compiled into a plot of mass or percentage of initial mass on the y axis versus either
temperature or time on the x-axis. This measurement provides information about physical phenomena,
such as phase transitions, absorption, adsorption and desorption; as well as chemical phenomena
including chemisorptions, thermal decomposition, and solid-gas reactions.

Thus STA can be used to measure the calorimetric signals as well as the weight change of a sample. Both
the systems (TG and DSC) can be operated using same software.

Technical Specification of equipment present in Ceramic Lab at Meta. Dept., COEP:

MODEL STA PT 1600

Temperature range:  RT to 1600°C
Heating rates: 0.01 up to 100°C/min
Sample weight: 5g
Resolution: 0.5 µg
Cooling rates: < 15min (1000°C – 100°C)
Detector: TG
TG – DSC
Sensor: S type
Electronics: integrated
Interface: USB

Experimental Procedure:

1. At the start of experiment, following points have to be taken care of: calibration, sample
preparation, sample weight, sample chamber temperature, reference material, temperature
program and atmosphere.
2. The tubular furnace is manually moved up so as to have the sample table visible. Put few mg of
sample powder in one of the two alumina crucibles. The sample is evenly distributed in the bottom
of the sample crucible. The other alumina crucible is left empty.
3. Use Linseis Acquisition software to fill in the data such as: weight of sample, measurement range,
corresponding zero curves to be followed (as they will do corrections in HDSC and TG data for the
sample), temperature profile or heating rate. Check that the temperature is at room temperature.
4. Get the cooling system “ON” and give the command to the software to start the program.

Observations:

The standard reference material for STA is calcium oxalate. The STA plots are as given in Fig. 2.
 Fig. 2 STA plots for Calcium Oxalate

The DTA curve for the decomposition of calcium oxalate monohydrate (CaC 2O4.H2O) in air is shown in
the diagram. The thermogram of calcium oxalate monohydrate has three peaks corresponding to the
successive elimination of H2O, CO and CO2. These three points of weight loss corresponds to the three
endothermic processes. However, the DSC data shows that the first and third reactions are purely
endothermic, as would be expected from a simple decomposition reaction. However, the second
reaction step shows evidence of two overlapping reactions, one endothermic and the other exothermic.
This can be explained by the Boudouard reaction, the equilibrium redox reaction of carbon monoxide
into carbon dioxide and carbon. At elevated temperatures that are less than 700°C, carbon monoxide
will react to form carbon and carbon dioxide, which is an exothermic reaction.

Some of the applications of STA are:

Table 2: Applications of STA

Adsorption Catalytic Reactions Compositional Analysis

Corrosion/Oxidation Crystallization Curing
Decomposition Differential Scanning Evaporation
Reactions Calorimetry
Glass Transition Magnetic Transitions Mass Changes
Temperature
Phase Diagrams Phase Transition Purity Determination
Temperatures
Reaction Kinetics Residual Mass Simultaneous Thermal
Analysis
Solid-Gas Reactions Solid-Liquid Reactions Solid-Solid Reactions
Specific Heat Sublimation Synthesis Reactions
Determination
Thermal Stability Thermogravimetric Transition Enthalpies
Analysis